JP2000080172A - Masterbatch resin pellet and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preparing masterbatch resin pellets containing a pigment and the like at high concentrations without being accompanied by strand breakage upon melt extrusion and generation of cuttings upon cutting strands, and masterbatch resin pellets obtained thereby. SOLUTION: Masterbatch resin pellets have a structure in which a core layer containing a thermoplastic resin and a compound (A) (a pigment and the like) is coated with a sheath layer containing a thermoplastic resin, and not less than 80% compound (A) is contained in the core layer. A method for preparing masterbatch resin pellets comprises melt extruding a melt containing a thermoplastic resin and a compound (A) as the core and a melt containing a thermoplastic resin as the sheath such that not less than 80% compound (A) is contained in the core to core-sheath type strands, cooling the strands and subsequently cutting the strand into pellets.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a masterbatch resin pellet having improved brittleness and a method for producing the same.

[0002]

2. Description of the Related Art Pigments; low molecular weight polymers such as wax; additives such as plasticizers, antioxidants, ultraviolet absorbers, and light stabilizers (hereinafter referred to as "pigments, etc.") are added to thermoplastic resins such as polystyrene, polyester, and polypropylene. Abbreviated as "), a method of adding these pigments and the like during the polymerization reaction, a method of adding a masterbatch in which the pigments and the like are dispersed or adhered to a polymer at a high concentration, to a natural resin,
Further, a method is known in which a pigment or the like is used as it is or a processed pigment comprising a pigment or the like and a dispersant such as low molecular weight polyethylene or metal soap is directly added to a polymer. Among these, the masterbatch is used in various fields from the viewpoint of easy handling at the time of addition and excellent performance (for example, non-staining property, suitability for automatic measurement, suitability for transportation).

[0003] A masterbatch contains a base resin as a main component, and a pigment and the like are kneaded into the base resin.
It is used after diluting 0-fold. In general, as the base resin of the masterbatch, the same or similar resin as the natural resin is used in view of the physical properties with the natural resin or the fluidity of the masterbatch. As a method for producing a masterbatch, a method is generally used in which a melt containing a base resin and a pigment is extruded into a strand, the strand is cooled, and the strand is cut into pellets.

[0004]

Considering that the masterbatch is diluted with a natural resin at the time of use,
Although it is desirable to contain pigments and the like in a high concentration, if a master batch containing a pigment in a high concentration is to be manufactured by a conventional method, the whole becomes brittle, so that the strand breaks during melt extrusion or cutting. The problem of the generation of swarf occurs. In addition, since additives generally have low compatibility with the base resin, if a master batch containing these at a high concentration is to be manufactured by a conventional method, the additives are likely to be unevenly distributed, and the location becomes brittle. Again, the problem of strand breakage during melt extrusion and generation of chips during cutting occurs.

Accordingly, an object of the present invention is to provide a method for producing a masterbatch resin pellet containing a pigment or the like at a high concentration without causing strand breakage during melt extrusion or generation of cutting chips during cutting, and can be obtained by the method. It is to provide a masterbatch resin pellet.

[0006]

Means for Solving the Problems In order to solve the above problems, the present invention provides the following configurations. (1) A masterbatch resin pellet obtained by blending at least one compound (A) selected from a pigment and an additive with a thermoplastic resin, wherein the core layer containing the thermoplastic resin and the compound (A) has a A masterbatch resin pellet with improved brittleness, having a structure covered with a sheath layer containing a plastic resin, wherein the core layer contains at least 80% by weight of the compound (A). (2) A method for producing a masterbatch resin pellet in which a thermoplastic resin is blended with at least one compound (A) selected from a pigment and an additive, wherein at least 80% by weight of the compound (A) is contained in a core. After being melted and extruded into a core-shell type strand with the melt containing the thermoplastic resin and the compound (A) as the core and the melt containing the thermoplastic resin as the sheath, after cooling the strand, , Cutting into pellets.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the conventional problem is solved by forming a strand to be melt-extruded into a core-sheath structure in which a brittle layer containing a compound (A) such as a pigment is covered with a tough layer on the outside. Was solved to improve brittleness. That is,
By making the core layer contain most (80% by weight or more) of the compound (A), the sheath layer becomes a tough layer containing little or no compound (A). It plays the role of a material and can prevent the occurrence of strand breaks during melt extrusion and cutting chips during cutting.

The core layer must contain at least 80% by weight of the compound (A), preferably at least 90% by weight, more preferably at least 95% by weight. When the ratio of the compound (A) contained in the core layer is less than 80% by weight,
Since the sheath layer contains a large amount of the compound (A), the sheath layer becomes brittle and cannot function as a reinforcing material.

The thickness of the strand to be melt-extruded is not particularly limited, but the diameter is preferably 0.5 to 5 mm, more preferably 2 to 4 mm. As a method of cooling the strand after the melt extrusion, a method of passing the strand through a cooling water tank is generally used. The master-batch resin pellets of the present invention can be obtained by cutting the cooled core-sheath type strand to a length of preferably 1.0 to 5.0 mm, more preferably 2.5 to 3.5 mm. The resin pellet of the present invention has a structure in which a core layer containing a thermoplastic resin and a compound (A) is covered with a sheath layer containing a thermoplastic resin, as in the case of the strand, and at least 80% by weight of the compound (A); Preferably, 90% by weight or more, more preferably 95% by weight or more, is contained in the core layer.

The ratio between the core layer and the sheath layer in the resin pellets of the present invention is not particularly limited. However, in order to exhibit the effects of the present invention, the weight ratio of the core layer to the sheath layer should be 50/50 to 50/50.
It is preferably in the range of 99/1, and 80/20 to 9
More preferably, it is in the range of 0/10. When the amount of the core layer is smaller than the above range, it becomes difficult to contain the compound (A) at a high concentration. On the other hand, if the sheath layer is less than the above range, the sheath layer is too thin to sufficiently fulfill the role of a reinforcing material.

The resin pellet of the present invention preferably contains a large amount of the compound (A), and the compounding amount of the compound (A) is 15% by weight or more for an organic pigment,
35% by weight or more for inorganic pigments, 25% by weight or more for additives of inorganic type, 5% by weight for organic type
It is preferable that it is above. Examples of the thermoplastic resin used in the present invention include polystyrene, polypropylene, polyethylene, AS resin, ABS resin, (meth) acrylic resin, vinyl chloride resin, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, polyolefin, and polyethylene terephthalate. , Polybutylene terephthalate, polyacetal, polycarbonate, polyamide,
Acetyl cellulose, fluororesin, polyester resin,
Examples include allyl resin, silicone resin, and thermoplastic elastomer. Among them, polystyrene, polypropylene, polyethylene, polyethylene terephthalate, and polyamide are preferable. These thermoplastic resins are used alone or in combination of two or more.

In the present invention, it is preferable to use the same or similar thermoplastic resin as the natural resin in view of the physical properties with the natural resin or the fluidity of the master batch. The plastic resins are also preferably the same or similar. The compound (A) used in the present invention is at least one selected from pigments and additives, and these compounds (A) are used alone or as a mixture of two or more.

As the pigment used in the present invention, any of known organic pigments, inorganic pigments, extender pigments and the like can be used. As organic pigments, insoluble azo, azo pigments such as condensed azo, anthraquinone, perinone, perylene,
Surenes such as thioindigo, phthalocyanine blue,
Examples include phthalocyanine-based phthalocyanine-based, naphthol green B, naphthol-green Y-based nitroso pigments, quinacridone-based, dioxazine-based, isoindolinone-based, pyrrolopyrrole-based, aniline black, and organic fluorescent pigments. As inorganic pigments, clay, baryte, natural products such as mica, graphite, chromate such as zinc yellow, barium yellow, ferrocyanide such as navy blue, sulfide such as zinc sulfide, sulfate such as barium sulfate, Oxides such as chromium oxide, zinc white, titanium white, red iron oxide, iron black and chromium oxide, hydroxides such as aluminum hydroxide, silicates such as calcium silicate and ultramarine blue, and carbonic acids such as calcium carbonate and magnesium carbonate Salt, carbon black, pine smoke, bone black,
Carbon such as graphite, aluminum powder, bronze powder,
Examples include metal powders such as zinc powder and other calcined pigments. Examples of the extender include extenders such as calcium carbonate, barium sulfate, and talc. These pigments are used alone or in combination of two or more. Dyes can also be used as long as the properties of the resin are not impaired.

The additives used in the present invention include resin physical properties (workability, flexibility, elasticity, brittleness, handleability, etc.), resin properties (stability, durability, flame retardancy, heat retention, etc.) and processing. It is used for the purpose of improving the properties (such as releasability and kneading properties) and is not particularly limited as long as it does not cause thermal decomposition when added to the molten resin. For example, plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, antibacterial agents, antistatic agents, copper damage inhibitors, metal deactivators, tackifiers, lubricants, slip agents, Internal release agent, anti-fogging agent (drip-proof agent, anti-fog agent), fragrance, surfactant, wetting agent, preservative, fungicide, filler, reinforcing agent, stabilizer, heat insulator, foaming Agents, anti-vibration agents, impact resistance improvers, surface treatment agents, warming agents, surface treatment agents, dispersants and the like.

Examples of the plasticizer used in the present invention include phthalate derivatives such as dimethyl phthalate, dibutyl phthalate, diethyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate and octyl decyl phthalate; dimethyl isophthalate, dioctyl isophthalate Phthalic acid isomers such as phthalate; tetrahydrophthalic acid derivatives such as di-2-ethylhexyltetrahydrophthalate; phosphate ester derivatives such as triphenyl phosphate, trichloroethyl phosphate, bisphenol A diphenyl phosphate; dimethyl adipate, dibutyl adipate, diisodecyl adipate; Adipic acid derivatives such as diisobutyl adipate;
Sebacic acid derivatives such as di-n-butyl sebacate, di-n-octyl sebacate, butylbenzyl sebacate; di-2
-Azelaic acid derivatives such as -ethylhexyl azelate, dimethyl azelate and dibenzyl azelate; citrates such as triethyl citrate, acetyl triethyl citrate and tributyl citrate; epoxidized soybean oil, butyl epoxy stearate, and epoxy stearic acid Epoxy such as octyl; Polyester such as polypropylene adipate and polypropylene sebacate;
Chlorinated systems such as chlorinated paraffins and chlorinated fatty acid esters; glycolic acid systems such as methylphthalylethyl glycolate and ethylphthalylethyl glycolate; tri-2-
Trimellitic acid such as ethylhexyl trimellitate; ricinoleic acid such as methyl acetyl ricinoleate and butyl acetyl ricinolate; butyl oleate; and the like, and one or more of these compounds may be used. Can be.

The antioxidants used in the present invention include:
2,6-di-t-butyl-p-cresol, pentaerythrityl-
Tetrakis- (3,5-di-t-butyl-4-hydroxyphenyl) propionate methylphenol, octadecyl-3
Phenolic compounds such as-(3,5-di-t-butyl-4-hydroxyphenyl) propionate; tris (2,4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, tetrakis ( Phosphorus such as 2,4-di-t-butylphenyl) -4,4'-biphenylenephosphonite;distearyl-3,3'-thiodipropionate, pentaeristol-tetrakis (3-laurylthiopro And the like, and one or more of these compounds can be used.

The ultraviolet absorber and light stabilizer used in the present invention include, for example, phenyl salicylate, pt-
Salicylic acid derivatives such as butyl salicylate; benzophenones such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole And benzotriazoles such as 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole; bis (2,2,6,6-tetramethyl-4-piperidyl) ) Sebacate, hindered amines such as dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, and the like. Among these compounds, One or more kinds can be used.

The flame retardant used in the present invention includes, for example, alkyl diallyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, triallyl phosphate, tributyl phosphate, triphenyl phosphate, tris (β-chloroethyl) phosphate, tris ( Phosphoric acid systems such as dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate and tris (bromochloropropyl) phosphate; chlorine systems such as chlorinated paraffin, chlorinated polyphenyl and perchloropentacyclodecane ; Tetrabromoethane, tetrabromobutane, hexabromobenzene, decabromodiphenyl oxide, polydibromophenyl oxide, bis (tribromophenoxy) ethane, ethylenebisdibro Norbornane dicarboximide, bromine such as ethylene bistetrabromophthalimide; chlorendic anhydride, tetrabromophthalic anhydride,
Tetrabromobisphenol A, diethoxy-bis- (2-
Reaction types such as (hydroxyethyl) -aminomethyl phosphate, dibromocresyl glycidyl ether and the like can be mentioned.
More than one species can be used. Further, a flame retardant stabilizer such as an epoxy stabilizer can be used in combination.

As the antibacterial agent used in the present invention, phenol ether fungicides having a phenol group in the molecular skeleton, such as 10,10'-oxybisphenoxaarsine, are exemplified as natural antibacterial agents. Having a tropolone central skeleton, for example, hinokitiol, β-
Drabulin and the like, as glycerin fatty acid esters, lower fatty acid monoglycerin ester, sucrose fatty acid ester, polyglycerin fatty acid ester, for example, caprylic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, palmitic acid sugar ester, decaglycerol monocaprate , Hexaglycerol monocaprylate and the like, as the zeolite-based compound, ion-exchangeable ions in the zeolite-based compound, for example, sodium ion, calcium ion,
Potassium ions, magnesium ions, ions having a part or all of antibacterial properties such as iron ions, for example, silver ions, copper ions, zinc ions, zeolitic compounds substituted with ammonium ions and the like, can be mentioned. One or more of them can be used.

The antistatic agent used in the present invention includes
For example, cationic systems such as quaternary ammonium chloride and quaternary ammonium sulfate; anionic systems such as alkyl sulfonate and alkylbenzene sulfonate; nonionic systems such as poly (oxyethylene) alkylamine and poly (oxyethylene) alkylamide; alkylbetaine Type, alkyl imidazoline type and other amphoteric systems; conductive resins such as polyvinyl benzyl type cations and polyacrylic acid type cations; and one or more of these compounds can be used.

Examples of the copper inhibitor and metal deactivator used in the present invention include 1,2,3-benzotriazole, tolyltriazole, tolyltriazoleamine salt, tolyltriazole potassium salt, and 3- (N-salicyloyl). ) Amino-1,2,4-triazole and the like, and one or more of these compounds can be used.

The tackifier used in the present invention includes:
For example, coumarone resin system such as a mixture of coumarone / indene resin, coumarone resin / naphthenic oil / phenol resin / rosin; pt-butylphenol / acetylene resin, phenol / formaldehyde resin, tempenphenol resin, polyterpene resin, xylene / formaldehyde resin, etc. Phenol / terpene resin type; Quinton A100 (manufactured by Zeon Corporation), Wingtack 95 (G
synthetic polyterpene resin system such as O.D.O. Chemical Co., Ltd.); aromatic hydrocarbon resin systems such as Nisseki Neopolymer 120, Nisseki Neopolymer 160 and Nisseki Neopolymer T; Escorez 1202U (manufactured by Exxon Chemical), E
aliphatic hydrocarbon resins such as scorez1271 (manufactured by Exxon Chemical), Tacchiroll 1000 (manufactured by Sumitomo Chemical), Tacchiroll 5000 (manufactured by Sumitomo Chemical), Piccole (manufactured by Hercules), etc .; Archon P-90
(Arakawa Chemical), Archon P-100 (Arakawa Chemical),
Alicyclic cyclic hydrocarbon resin systems such as Heylets G-100X (manufactured by Mitsui Petrochemical) and Heylets T-100X (manufactured by Mitsui Petrochemical); aliphatic and alicyclic petroleum resin systems such as Escorez 1401 (manufactured by Exxon Chemical); Escore
z2101 (manufactured by Exxon Chemical), Escorez220
Aliphatic aromatic petroleum resin such as No. 3 (manufactured by Exxon Chemical);
Unsaturated hydrocarbon polymer systems such as Escorez 8030 (manufactured by Exxon Chemical); hydrogenated hydrocarbon resin systems such as Escorez 5380 (manufactured by Exxon Chemical) and Escorez 5300 (manufactured by Exxon Chemical); YS Resin 75
(Made by Yashara Chemical), Piccotac resi
hydrocarbon-based tackifying resin such as nsA (manufactured by Hercules); polybutene, atactic polypropylene, liquid polybutadiene, cis-1,4-polyisoprene rubber, hydrogenated polyisoprene rubber, Claprene LIR-290
Petroleum hydrocarbon resins such as (Kuraray); pentaerythritol ester of rosin, glycerol ester of rosin, hydrogenated rosin, methyl ester of advanced rosin, methyl ester of hydrogenated rosin, triethylene glycol ester of hydrogenated rosin Pentaerythritol ester of hydrogenated rosin, hydrogenated rosin ester, high melting point ester resin, polymerized rosin, zinc resinate,
Rosin derivatives such as cured rosin; turpentine tackifiers, co-condensates of synthetic resins and phthalates, nonionic activators, etc., and one or more of these compounds can be used. Can be.

The lubricant and slip agent used in the present invention include, for example, paraffin waxes such as liquid paraffin, natural paraffin, microwax, polyethylene wax, chlorinated paraffin, fluorocarbon and synthetic paraffin; stearic acid, palmitic acid, myristic acid Amides such as fatty acids, behenic acid and arachidin; aliphatic amides such as aliphatic amides and alkylenebisfatty acid amides; lower alcohols such as butyl stearate; esters such as polyhydric alcohols, polyglycol esters and higher alcohol esters. Metal soaps such as magnesium stearate, calcium stearate and lonozinc; polyhydric alcohols such as fatty alcohols, ethylene glycol, diethylene glycol and triethylene glycol; Fatty acid and partial esters of polyhydric alcohols, such as fatty acids and partial esters of polyglycol polyglycerol can be mentioned, can be used one or two or more of these compounds.

The internal release agent used in the present invention includes:
For example, perfluoroalkyl betaine, perfluoroalkyl ethylene oxide adduct, ether-type phosphoric acid ester, synthetic organic acid ester derivative, nonionic activator and the like can be used. One or more of these compounds are used. Can be. Examples of the anti-fogging agent (drip-proofing agent, anti-misting agent) used in the present invention include, for example, Mar
k39 (manufactured by Adeka Argus Chemical), Rheodol SP-
P10 (manufactured by Kao), Rheodol SP-O10 (manufactured by Kao), AD-339 (manufactured by Sakai Chemical), Rheostat SS-
Sorbitan fatty acid esters such as No. 60 (manufactured by Lion), Limacale P-300 (manufactured by RIKEN Vitamin Co.), Limacale S-300 (manufactured by RIKEN Vitamin Co.), and Limacale O-250 (manufactured by RIKEN Vitamin Co.); Fatty acid diethanolamides such as Fine Chemical Co., Ltd., Amizole ODE (Kawaken Fine Chemical Co., Ltd.); Resist AF101 (Daiichi Kogyo Seiyaku), Register 8200 (Daiichi Kogyo Seiyaku), Antox D
FM (manufactured by Nippon Emulsifier), PA-1743 (manufactured by Marubishi Yuka), PA-5221 (manufactured by Marubishi Yuka), Denone 4190
(Manufactured by Marubishi Yuka), Rheostat DGS (B) (manufactured by Lion), Limacale S-105 (manufactured by Riken Vitamin Co.), Limacale S-120 (manufactured by Riken Vitamin Co.), polyethylene glycol monooleate, polyethylene glycol monolaurate And the like, and one or more of these compounds can be used.

As the fragrance used in the present invention, for example, Alamask AF (manufactured by Rhone Poulin), Al
amaskAO (Rhone-Poulenc), Alama
skCY (Rhone Poulin), AlamaskH
(Available from Rhone-Poulenc), AlamaskAA (Available from Rhone-Poulenc), AlamaskH (Available from Rhone-Poulenc), AlamaskND (Available from Rhone-Poulenc), Rodo No. 0 (manufactured by Vanderbilt), R
odo No. 4 (Vanderbilt), Rodo
No. 10 (manufactured by Vanderbilt), sodium borohydride, lithium borohydride, phthalic anhydride, peroxides such as sodium perborate, vanilla essence, and the like. One or more of these compounds can be used. Can be used.

The surfactant used in the present invention includes:
For example, carboxylate, fatty acid salt, cyclic fatty acid salt, special polycarboxylate type activator, sulfonate, alkyl or alkenyl sulfonate, alkyl allyl sulfonate, polycondensate of alkyl allyl sulfonate, sulfate ,
Alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, phosphate, alkyl phosphate, polyoxyethylene alkyl (phenyl) ether phosphate, inorganic phosphate Anionic surfactants such as polyoxyethylene derivatives, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene polyoxypropylene blocks Nonionic surfactants such as polymers, polyoxyethylene alkylamines, polyoxyethylene alkylamides, and polyhydric alcohol derivatives; alkylamine salts,
Cationic surfactants such as quaternary ammonium salts; amphoteric surfactants such as alkyl betaine; fluorine-based surfactants, silicon-based surfactants, and reactive surfactants. From 1 or 2
More than one species can be used.

Examples of the wetting agent used in the present invention include alkyl naphthalene sulfonate, alkyl sulfosuccinate, sulfate, polyoxyethylene derivatives such as ADEKATOL NP-675 (manufactured by Asahi Denka), and Hyonic D.
E series (manufactured by San Nopco), Nopco 2272-R-
SN (manufactured by San Nopco), Nopco Wet 50 (manufactured by San Nopco), and the like, and one or more of these compounds can be used.

The preservatives and fungicides used in the present invention include, for example, pentachlorophenol, p-chloro-m
-Xylenol, dehydroobiethylamine pentachlorophenol (Hercury), 4-chloro-2-phenylphenol, N- (trichloromethylthio) phthalimide, N-dimethyl-N'-phenyl- (N'-fluorodichloromethylthio) sulfamide , N- (trichloromethylthio)
-4-chlorohexene-1,2-dicarboximide, 2,4,5,6-
Organochlorine compounds such as tetrachloro-iso-phthalonitrile; organocopper compounds such as copper-8-quinolinolate; organotin compounds such as bis (tri-n-butyltin) oxide, tributyltin laurate and tributyltin chloride; 10,10'-oxybisphenoxacin (manufactured by Ventron), Vinygene SB-1 (Morton Th)
iokol), Vinygene SB-5-2 (M
organic arsenic compounds such as Orton Thiokol); quarternary ammonium carboxylate (manufactured by Rohm &Haas); 2- (4-thiazolyl) benzimidazole; and one of these compounds. Alternatively, two or more kinds can be used.

The filler used in the present invention includes alumina, antimony trioxide, asbestos, barite, calcium carbonate, anhydrite, kaolin clay, carbon black, diatomaceous earth, feldspar powder, acid clay, quartz, graphite, carbonate Magnesium, magnesium hydroxide, magnesium oxide, mica, molybdenum disulfide, lauric clay,
Sericite, finely divided silica, silica side, slate powder,
Talc, titanium oxide, vermiculite, volcanic ash, whitening, precipitated calcium carbonate, heavy calcium carbonate,
Examples thereof include hydrated silicic acid, silicic anhydride, hydrated silicate, kaolin clay, hard clay, calcined clay, and finely divided talc. One or more of these compounds can be used.

Examples of the reinforcing agent used in the present invention include glass thread, roving, chopped strand, chopped strand mat, glass cloth, glass tape, roving cloth, and milled fiber. Species or two or more can be used. In the present invention, a so-called water-inhibiting material can be used as an additive. A water-inhibiting material is a material that loses its inherent properties as an additive when it reacts with water or comes into contact with water.
The strand after melt extrusion is usually cooled by passing through a water bath, but it was impossible to produce a masterbatch containing a water-inhibiting material by this method. However, according to the present invention, a water-inhibiting material is mainly used for the core layer, and a water-inactive thermoplastic resin is used for the sheath layer. Can be. Such water-inhibiting materials include a moisture absorbent, an oxygen generator, a carbon dioxide generator, an ethyl alcohol generator,
Examples thereof include a sulfurous acid gas generator and an oxygen absorber.
Examples of the hygroscopic agent include silica gel, aluminum oxide, synthetic zeolites represented by molecular sieves, natural zeolites such as mordenite and erionite, perlite, viscous minerals such as acid clay and activated clay, porous glass,
Magnesium silicate, aluminum silicate, polymer adsorbent,
Activated carbon, activated carbon fiber, molecular sieving carbon, bone charcoal, calcium oxide, calcium silicate, calcium chloride, calcium bromide, barium oxide, barium bromide, barium perchlorate, magnesium chloride, magnesium oxide, magnesium sulfate, perchloric acid Magnesium, aluminum sulfate, sodium sulfate, sodium hydroxide,
Examples thereof include sodium carbonate, potassium carbonate, potassium hydroxide, zinc chloride, zinc bromide, and lithium perchlorate. Examples of the oxygen generator include sodium carbonate hydrogen peroxide adducts, calcium peroxides, and magnesium peroxides. Examples of the carbon dioxide generator include carbonate-organic acid-based, carbonate-amino acid-based and carbonate-inorganic acid-based carbon generators. As the ethyl alcohol generator, for example, there is an ethyl alcohol generator embedded in a water-soluble component as disclosed in Japanese Patent Publication No. 1-57947. Examples of the sulfur dioxide generating agent include, for example, JP-A-52-44252.
And sodium bisulfite and sodium pyrosulfite disclosed in JP-A-62-232332. As the oxygen absorbent, Japanese Patent Publication No. 58-290
No. 69 discloses a metal powder-based oxygen absorber such as iron powder and an ascorbic acid-based oxygen absorber. As the thermoplastic resin which is inert to water and which can be used for the sheath layer, among the thermoplastic resins exemplified above, polyolefin resins such as polypropylene and polyethylene are preferable.

Among these additives, UV absorbers, antistatic agents, light stabilizers, slip agents, lubricants, etc., which have low compatibility with resins, inorganic flame retardants, fillers, antibacterial agents, etc. are particularly brittle. For this reason, it was difficult to use a large amount in some conventional techniques, and it is very effective to make the core-sheath structure into a strand shape according to the present invention. The masterbatch resin pellet of the present invention is added to and blended with an intended natural resin to form a molded product. As a molding method of a molded article, for example, an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, an inflation molding method, a calendar molding method, a slash molding method, a dip molding method, a foam molding method, and the like can be employed. it can.

[0032]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 HI-PS resin in powder form (MI = 5,
27.8 parts by weight of specific gravity 1.05)
7 μm, oil absorption 24 g / 100 g) 72.2 parts by weight were previously mixed with a 75 L mixer and supplied to a triple twin screw extruder (46 mm, L / D = 30) to obtain the same type of pellet-like HI-PS resin. Is a single screw extruder (30 mm, L /
D = 22). Temperature from each extruder
It is supplied to a core-sheath type die (four bases) at 0 ° C., and the four extruded strands are passed through a water bath, cooled and cut with a pelletizer, and the outer diameter is 3 mm and the sheath thickness is 0.15 mm.
Was obtained. The core / sheath ratio of this master batch was core / sheath = 9/1 (weight ratio), and the pigment concentration in the master batch was 65% (weight ratio). At this time, a high-concentration pigment master batch resin pellet having a uniform shape could be obtained without generation of strand breaks during extrusion and cutting chips during cutting. [Comparative Example 1] 35 parts by weight of the powdery HI-PS resin and 65 parts by weight of a valve stem same as in Example 1 were mixed with a 75 L mixer and supplied to a three-row twin screw extruder (46 mm, L / D = 30). The core alone was fed to a core-sheath die at a temperature of 210 ° C. The extruded strand was low in strength and often suffered from strand breakage, and could not be industrially produced. Example 2 Powdery polyester resin (Homo PE
T, IV = 0.75) 55.6 parts by weight and carbon black (average particle size 25 nm, DBP oil absorption 70 cc / 100)
g) 44.4 parts by weight are mixed in advance with a 75 L mixer, and a three-row twin screw extruder (46 mm, L / D = 30)
And the same type of pelletized polyester resin (homoPET) was supplied to a single screw extruder (30 mm, L / D = 22). Each extruder supplies the core-sheath type die (four bases) at a temperature of 280 ° C., cools the four extruded strands through a water tank, cuts them with a pelletizer, and has an outer diameter of 3 mm and a sheath thickness of 0.1 mm. Was obtained. The core / sheath ratio of this master batch is
The sheath was 9/1 (weight ratio), and the carbon black concentration in the master batch was 40% (weight ratio). At this time, a high-concentration pigment master batch resin pellet having a uniform shape could be obtained without generation of strand breaks during extrusion and cutting chips during cutting. Comparative Example 2 60 parts by weight of a powdery polyester resin (homoPET) and carbon black 40 as in Example 2
Parts by weight were mixed with a 75 L mixer, and a 3-row twin screw extruder (46
φmm, L / D = 30) and temperature is 280 only at the core
C. and fed to a core-sheath die. The extruded strand was low in strength and often suffered from strand breakage, and could not be industrially produced. Example 3 85 parts by weight of a powdery 6 nylon resin and 15 parts by weight of a lubricant (ethylene bisstearic acid amide) were mixed with a double feed twin screw extruder (35 φm) using a weight feeder.
m, L / D = 32), and the same type of pellet-like 6 nylon resin is fed into a single screw extruder (30 mm, L / D = 22).
Supplied. The extruders were supplied at a temperature of 220 ° C. to a core-sheath type die (four bases) at a temperature of 220 ° C., and the four extruded strands were passed through a water tank, cooled, cut with a pelletizer, and had an outer diameter of 3 mm and a sheath thickness of 0.15 mm. Was obtained. The core / sheath ratio of this master batch was core / sheath = 8/2 (weight ratio), and the lubricant concentration in the master batch was 12% (weight ratio). At this time, there was no generation of strand breaks during extrusion or cutting chips during cutting, and it was possible to obtain a lubricant high-concentration master batch resin pellet having a uniform shape. [Comparative Example 3] 88 parts by weight of the same powdery nylon 6 resin and 12 parts by weight of a lubricant as in Example 3 were fed to a twin-screw twin-screw extruder (35 mm, L / D = 32) using a weight feeder, and the core was fed. Alone and fed to a core-sheath die at a temperature of 220 ° C. The extruded strand was low in strength and often suffered from strand breakage, and could not be industrially produced. Example 4 A pellet-shaped polypropylene resin (Homo P
P, MI = 8) 17 parts by weight, 40 parts by weight of quinacridone red previously processed with a pigment and a low molecular weight polyethylene resin with three rolls and the like, and a low molecular weight polyethylene resin 60
40 parts by weight of a processed pigment (master powder) in which parts by weight were previously kneaded with three rolls and the like and 43 parts by weight of a master powder containing 50 parts by weight of isoindolinone were mixed by a tumbler, and a twin-screw extruder was used. (35 mm,
L / D = 32) and the same kind of pellet-like polypropylene (homo PP) was fed to a single screw extruder (30 mm, L / D
= 22). 180 temperature from each extruder
At 4 ° C, it was fed to a core-sheath type die (four bases) and extruded.
The strand was cooled by passing through a water tank and cut with a pelletizer to obtain a master batch having an outer diameter of 3 mm and a sheath thickness of 0.2 mm. The core / sheath ratio of this master batch was core / sheath = 8/2 (weight ratio), and the pigment concentration in the master batch was 30% (weight ratio). At this time, a high-concentration pigment master batch resin pellet having a uniform shape could be obtained without generation of strand breaks during extrusion and cutting chips during cutting. Comparative Example 4 A master powder containing 33.6 parts by weight of the same pellet-shaped polypropylene resin (homo-PP) as in Example 4, and 40 parts by weight of quinacridone red obtained by previously processing a pigment and a low molecular weight polyethylene resin with three rolls or the like was used. As with 32 parts by weight, 34.4 parts by weight of a master powder containing 50 parts by weight of isoindolinone was mixed with a tumbler and supplied to a twin-screw twin-screw extruder (35 mm, L / D = 32). C. and fed to a core-sheath die. Extruded strands have a so-called surging phenomenon, and the thickness of the strands is not constant, making it impossible to form a masterbatch with a uniform shape. Production was impossible.

[0033]

According to the present invention, a masterbatch resin pellet containing a pigment or the like at a high concentration can be produced without causing strand breakage during melt extrusion or cutting chips during cutting.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 (72) Inventor Hiroyuki Mori 1-35 Morimoto, Itami-shi, Hyogo Prefecture Sumika Karaー F-term in Osaka Factory Co., Ltd. 4J002 AB021 AE052 BA012 BB031 BB121 BC031 BC061 BD041 BD101 BD121 BE021 BE061 BF021 BG001 BK002 BN151 CC032 CD162 CF061 CF071 CG001 CL001 CP031 EB047 EE037 EE047 EH097 EH147 EJ017 EL137 EU177 EV047 EV097 EW047 EW067 FD01 FD022 FD027 FD057 FD077 FD096 FD107 FD137 FD177 FD187 FD202 FD207 FD31

Claims (3)

[Claims] 1. A masterbatch resin pellet comprising a thermoplastic resin and at least one compound (A) selected from a pigment and an additive, wherein the core layer containing the thermoplastic resin and the compound (A) is A masterbatch resin pellet having improved brittleness, which has a structure covered with a sheath layer containing a thermoplastic resin, wherein the core layer contains at least 80% by weight of the compound (A). 2. The weight ratio between the core layer and the sheath layer is 50 / 50-9.
2. The masterbatch resin pellet according to claim 1, which is in the range of 9/1. 3. A method for producing a masterbatch resin pellet comprising mixing a thermoplastic resin with at least one compound (A) selected from a pigment and an additive, wherein 80% by weight or more of the compound (A) is used. So that it is included in the core,
Using a melt containing a thermoplastic resin and a compound (A) as a core, using a melt containing a thermoplastic resin as a sheath, melt-extruding into a core-sheath type strand, cooling the strand, and then cutting the pellet into pellets. The manufacturing method characterized by the above-mentioned.